Caulking composition comprising polymer having addition polymerized backbone having carboxyl groups esterified with drying oil fatty acid glycidyl ester

ABSTRACT

THE CAULKING OR SEALING COMPOSITION OF THE INVENTION HAS AS ITS BINDER AN ACRYLIC BACKBONE CONTAINING PENDANT UNSATURATED GROUPS, PREFERABLY DERIVED FROM DRYING OILS OR EQUIVALENT AIR CURABLE UNSATURATED PENDANT ALKYL RADICALS, AND ATTACHED TO THE ACRYLIC BACKBONE THROUGH ESTER LINKAGES. THE MODIFIED ACRYLIC PRODUCT HAS THE FEXIBILITY AND DURABILITY CHARACTERISTIC OF ACRYLICS, AND THE ADVANTAGE THAT THE COMPOSITION WILL CURE SIMILARLY TO DRYING OILS, USING DRIERS SUCH AS COBALT NAPHTHENATE AND ZINC NAPHTHERNATE.

United States Patent CAULKING COMPOSITION COMPRISING POLY- MER HAVINGADDITION POLYMERIZED BACKBONE HAVING CARBOXYL GROUPS ESTERIFIED WITHDRYING OIL FATTY ACID GLYCIDYL ESTER William D. Emmons, HuntingdonValley, Pa., assignor to Rohm and Haas Company, Philadelphia, Pa. NoDrawing. Filed Sept. 7, 1971, Ser. No. 178,429 Int. Cl. C08g 51/02,51/04 US. Cl. 260-41 A 4 Claims ABSTRACT OF THE DISCLOSURE Thisinvention relates to caulking, sealing, or putty compositions.

There are many types of caulking compounds including those in which thebinder is such that they are surface drying. This includes drying byoxidation or by solvent release. The permanently plastic binderscomprise another category. Other types of caulking compounds are thosewhich are catalytically cured and those which are heat convertible. Thedisadvantage of the drying oil type, which drys by oxidation, is thatthe oil may bleed from the composition, before it is cured, be absorbedby porous substrates such as Wood, and ultimately the drying reaction iscarried to such an extent that the products become brittle and sometimesextremely hard. This makes replacement of the caulking very difficult.

The present invention provides a combination of types of cure andprovides a combination of properties which could be said to be apermanently plastic product which cures by an oxidation reaction ofunsaturated groups on the permanently plastic polymer, and preferablyalso by solvent evaporation. Basically, the product comprises anaddition polymer backbone such as an acrylic backbone which has groupsattached thereto through esterification of carboxyl groups on thebackbone by a fatty acid glycidyl ester, the fatty acid having anunsaturated group curable by a drying or oxidative mechanism. The binderfor the caulking compound has units of the following structure:

.QLEZLiLlfELiLl wherein R is H, lower alkyl of up to about 4 carbons,such as methyl or butyl, or less preferably halogen,

CH COOR,

3,786,020 Patented Jan. 15, 1974 -COOR, or CH COOH, R being lower alkylof from 1 to 8 carbon atoms;

R being at least one of H and at least one lower alkyl having from 1 to8 carbon atoms; examples being methyl, hexyl, and octyl, at least aportion of R being H to give free carboxyl groups;

R is an unsaturated air curable alkyl radical having up to about 22carbon atoms, preferably from a drying oil fatty acid, and preferably aminimum of about 10 carbons;

R is H, COOH, CONH or -COOR, wherein R is as above, R preferably beingH; and

X is derived from at least one copolymerizable optional vinyl monomer(defined hereinbelow) other than the one or ones from which the righthand parenthetical group Lilli l l is] is derived. It is to beunderstood that when R and/or R contain a free carboxyl group (COOH),the glycidyl ester will react therewith to give pendant ester groupsequivalent to the structure of Formula V, below.

The units in parentheses are in any order.

Examples of R and R are:

Acid for carboxyl R R source Acrylic.

Methacrylie.

Maleic, fumaric.

- Maleamic.

Cl Ghloromaleic. CHzCOOCH; H Methyl acid itaconate. CHZCOOH H Itaeonic.013200011"--- OOOH Aeonitie. H C O 0 CH3 Methyl acid maleate.

alibi l (5R III and the glycidyl ester has the formula 9 CI- z-OHCHz0f3R IV wherein the symbols used have the same meaning as givenabove.

An essential characteristic of the ultimate elastomeric polymer obtainedby esterifying pendant -COOH groups of the backbone by reaction with theunsaturated glycidyl ester, as concerns caulks, is that there be lessthan about 10 percent, and more preferably less than about 5 percent, ona weight basis, of the groups represented by the formula:

If this criterion is not observed, over a long period of time the caulkmay become too brittle or hard for proper expansion and contraction ofabutting surfaces in contact with a single caulk bead, or the bead maybecome so hard as to preclude easy repair. Without a silane of the typeused in solvent-based caulks, wet adhesion on upright surfaces may bedefective, especially if more than 5 percent of said groups by weight ispresent. For proper adhesion of the caulk and for other advantageousproperties, it is essential to have free carboxyl groups along with thependant ester groups.

The backbone polymer is a water-insoluble vinyl polymer containing therequisite proportion of free carboxyl (COOH) groups as described herein.

The proportions of monomers in the backbone are such that there is atleast 0.25 percent and no more than 25 percent of unsaturated carboxylicacid, by weight, in the monomers going into said backbone polymer. Apreferred range is from about 1 percent to 5 percent, and the optimum isconsidered to be in the range of 1.5 percent to 3.5 percent. In reactingthe glycidyl ester of the unsaturated fatty acid with free carboxyl(COOH) groups in the backbone polymer, the mole ratio of is in the rangeof from 1:02 to 1:0.9, preferably from 1:0.3 to 1:0.7. A particularlyuseful range is from 1:0.4 to 1:06. It is essential to have asubstantial proportion of free carboxyl groups for proper adhesion and,for maximum long-term flexibility necessary in the cured caulks, aminimum of the drying oil functionality.

Hard monomers such as styrene or methyl methacrylate are useful in therange of to 90 percent, preferably to percent, with soft monomers suchas ethyl or butyl acrylate forming from about 75 percent to about 99.75percent of the total monomers, preferably 70 to 94 percent.

As stated above, the backbone polymers are those of vinyl additionpolymer type, including as an essential component the a ti-unsaturatedcarboxylic acid, preferably acrylic acid or methacrylic acid. Otheruseful copolymerizable acids are named in US. Pats. Nos. 3,098,760 and3,261,796, additional examples being given below.

To amplify, the unsaturated carboxylic acid may be a simplemonocarboxylic acid, a polycarboxylic acid, or may be a partial ester orhalf amide of such O S-unsaturated polycarboxylic acids, and saltsthereof with a volatile base such as ammonia, or with a volatilewater-soluble amine such as dimethylamine, triethylamine,triethanolamine, morpholine, N-methyl morpholine, picoline, and thelike. Examples of copolymerizable ethylenically unsaturatedmonocarboxylic or polycarboxylic acids are sorbic, acryloxyacetic,acryloxypropionic, cinnamic, vinyl furoic, u-chlorosorbic,methacryloxypropionic, methacryloxyacetic, p-vinylbenzoic, acrylic,methacrylic, maleic, fumaric, aconitic, atropic, crotonic, and itaconicacid, or mixtures thereof, with itaconic acid and the afi-HHSEltUfatedmonocarboxylic acids, particularly methacrylic acid and acrylic acid,being preferred. Other copolymerizable acid monomers include the alkylhalf esters or partial esters of unsaturated polycarboxylic acids suchas of itaconic acid, maleic acid, and fumaric acid, or the partialamides thereof. Preferred half esters are the lower alkyl (C to C esterssuch as methyl acid itaconate, butyl acid itaconate, methyl acidfumarate, butyl acid fumarate, methyl acid maleate, and butyl acidmalete. Such partial esters and partial amides are considered to beS-unsaturated monocarboxylic acids, and the term as used herein includessuch esters and amides.

The term vinyl monomer as used herein means a monomer comprising atleast one of the following groups:

vinylidene: CH :C vinyl: CH =CH-, and vinylene: CH=CH,

whether homopolymerizable or not, giving units corresponding to X and toFormula II. Examples are the 11,13- ethylenically unsaturatedmonocarboxylic acids and esters and amides thereof, a ti-ethylenicallyunsaturated aldehydes, a ti-ethylenically unsaturated dicarboxylic acidsand esters, amides, half esters, and half amides thereof, a,B-ethylenically unsaturated nitriles, hydrocarbons such as oc-OlCfiIIS,conjugated diolefins, vinylaryl compounds, vinyl alkyl ethers, vinylhalides, vinylidene halides, vinyl sulfides, vinyl acyloxy compounds(esters of saturated carboxylic acids and ethylenically unsaturatedalkanols), vinyl amines and salts thereof, vinyl ureido monomers, -vinylcompounds having heterocyclic nitrogen-containing (HN groups, andhalogen, hydroxyalkyl, or aminoalkyl substituted derivatives thereof,whether homopolymers or copolymers. The vinyl polymers and methods fortheir preparation form no part of the present invention, and any suchpolymer may be treated in accordance with the present invention. Forexamples of well-known vinyl polymers and methods of preparing the same,see Polymer Processes, Schildknecht, Interscience, N.Y. (1956), pp.111-174. Mixtures of different polymers are useful.

Specific examples of suitable monomers which may be copolymerized toobtain the water-insoluble polymers for use according to the inventionin addition to the unsaturated acid monomers and esters thereof withalkanols having 1 to 20 carbon atoms, such as methanol, ethanol,butanol, pentadecanol and the like, are acrolein, methacrolein,ethylene, propylene, isobutene, butadiene, isoprene, chloroprene,styrene, vinyl-toluene, vinyl methyl ether, vinyl isobutyl ether, vinylchloride, vinyl bromide, vinylidene chloride, vinyl sulfide, vinylacetate, vinyl propionate, 'the vinyl pyridines, primary amino compoundssuch as B-aminoethyl vinyl ether, aminopentyl vinyl ether, secondaryamino-containing compounds such as secondary amyl tbutyl aminoethylmethacrylate, tertiary aminocontaining compounds such ast-dimethylaminoethyl methacrylate, and the allied amine salts such asthe chloride or hydroxide, ureido monomers such as are disclosed in US.Pats. Nos. 2,881,155 to Hankins, 3,300,429 to Glavis and Keighly, and3,356,627 to Scott, examples bemg fl-ureid'oethyl acrylate,fi-(N,N'-ethyleneureido)ethyl acid maleate, fl-ureidoethyl vinyl ether,N-vinyl-N,N'- ethyleneurea, N vinyloxyethyl N,N'-ethyleneurea, N-methacrylamidomethyl N,N' ethyleneurea, and N-dimethylaminoethyl N vinylN,N' ethyleneurea, B- hydroxyethyl meth-acrylate,N-hydroxyethylacrylamide, N methylolacrylamide, and N(dimethylaminoethyl) acrylamide. Copolymers, and graft, block, orsegmented polymers are included. Conventional methods of obtaining thebackbone polymers are utilized.

As is described below, these vinyl monomers include the acids mentionedabove and esters thereof, as well as known soft and hard monomers.

Another of the important, and at times essential monomers, in additionto the acid monomer, usually utilized in a substantial proportion toprepare the backbone polymer is a resiliency-imparting or soft monomerwhich may be represented by the following formula:

R g II 11 CO R wherein R is H or alkyl having 1 to 4 carbon atoms and Ris the straight chain or branched chain radical of a primary orsecondary alkanol, al'koxyalkanol or alkylthiaalkanol, and having up toabout 14 carbon atoms, examples being ethyl, propyl, n-butyl,Z-ethylhexyl, heptyl, hexyl, octyl, propyl, Z-methylbutyl,l-methylbutyl, butoxybutyl, 2 methylpentyl, methoxymethyl, ethoxyethyl,cyclohexyl, n-hexyl, isobutyl, ethylthiaethyl, methylthiaethyl,ethylthiapropyl, n-octyl, 6-methylnonyl, decyl, dodecyl, and the like,said radicals R when alkyl, having from 2 to about 14 carbon atoms,preferably from 3 to 12 carbon atoms, when R is H or methyl. When R isalkyl and R is alkyl, R should have from about 6 to about 14 carbonatoms and when R is H and R is alkyl, R should have from about 2 toabout 12 carbon atoms, in order to qualify as a soft monomer.

Other ethylenically unsaturated copolymerizable vinyl monomers, thehomopolymers of which have a much higher T,,, are used in combinationswith the above mentioned soft monomers provided they do not adverselyaffect the desired properties of the caulk (e.g., unduly raise theoverall T The hard acrylics may be represented by the formula wherein Ris as above. R is preferably alkyl and is methyl or alkyl having fromabout 13 to about 20 carbon atoms when R is H, and is alkyl of from 1 toabout carbon atoms or alkyl of from about 15 to about 20 carbon atomswhen R is methyl. It can be seen from above that for alkyl acrylates andalkyl methacrylates the T at first decreases with an increased chainlength of the alkyl group and then the T again increases; i.e., bothhard and soft monomers are known to occur in each group of monomers.Examples of these hard monomers and other hard monomers include: methylacrylate, acrylamide, vinyl acetate, tetradecyl acrylate, pentadecylacrylate, methyl methacrylate, ethyl methacrylate, t-butyl acrylate,butyl methacrylate, styrene, pentadecyl methacrylate, vinyl toluene,methacrylamide, and N-methylolacrylamide.

As is known, for a given number of carbon atoms in the alcohol moiety,the extent and type of branching markedly influences the T the straightchain products giving the lower T As is apparent, an important propertyof the backbone polymer is the T thereof, and consequently the selectionof monomers and proportions thereof depends upon their influence on theT The T of the polymer must be below C., preferably below 0 C. (i.e., itmust give a rubbery product) and is more preferably below 10 C. Themodified backbone polymer containing the pendant ester groups must alsohave the same T requirements. T is a conventional criterion of polymerhardness and is described by Flory, Principles of Polymer Chemistry, pp.56 and 57 (1953), Cornell University Press. See also Polymer Handbook,Brandrup and Immergut Sec. III, pp. 61-63, Interscience (1966). Whileactual measurement of the T is preferred, it may be calculated asdescribed by Fox, Bull. Am. Physics Soc. 1, 3, p. 123 (1956). Examplesof the T of homopolymers and the inherent T, thereof which permits suchcalculations are as follows: 1

6 Homopolymer of: T C. n-octyl acrylate n-decyl methacrylate -602-ethylhexyl acrylate 70 n-butyl acrylate -56 octyl methacrylate 20n-tetradecyl methacrylate -9 methyl acrylate 9 n-tetradecyl acrylate 20t-butyl acrylate 43 methyl methacrylate acrylic acid 106 These or othermonomers are blended to give the desired T of the copolymer.

The polymeric backbone is desirably obtained by solution polymerizationof one or more of the ethylenically unsaturated acids with otherunsaturated monomers including, among the more preferred vinyl monomers,the esters of acrylic acid or methacrylic acid with benzyl alcohol,phenol, or a saturated monohydric aliphatic alcohol, especially analkanol, having 1 to 18 carbon atoms, such as cyclopentanol,cyclohexanol, methanol, ethanol, n-propanol, isopropanol, n-butanol,methoxyethanol, ethoxyethanol, methoxyethoxyethanol,ethoxyethoxyethanol, isobutanol, sec-butanol, tert-butanol, any of thepentanols, hexanols, octanols, decanols, dodecanols, hexadecanols, andoctadecanols, bearing in mind the required T and acid monomer. Otherpreferred comonomers include acrylonitrile, methacrylonitrile, vinylacetate, styrene, vinyl toluene (o, m, or p), vinyl chloride orvinylidene chloride.

Particularly preferred are polymers predominantly of an ester of acrylicacid and an alkanol having 1 to 4 carbon atoms, copolymerized with anester of methacrylic acid and an alkanol having 1 to 4 carbon atoms,methacrylonitrile or acrylonitrile, with methacrylic acid or acrylicacid being copolymerized in smaller amounts. Blends of copolymers may beused.

High molecular weight polymers, e.g., 10,000 to several million,obtained by emulsion or solution polymerization or other methods, and ofwater-insoluble character when in acid form, are used as the backbonepolymer. Preferably, the backbone polymer has a molecular weight of10,000 to 600,000 or more.

The substrates with which the invention is concerned are all typesincluding siliceous substrates such as glass sheets, fiberglasstextiles, asbestos sheets, asbestos cement products, concrete, stone,stucco, slate, sandstone, granite, ceramics, and porcelain; also fiberreinforced plastic articles such as canoes, boathulls, or other formedarticles made out of fiber-glass reinforced polyesters or other plasticmaterials; metals such as aluminum, steel, iron, brass; wood and otherstructural materials; metal oxide layers such as those of aluminum oxideand iron oxide; leather; textiles of cellulose such as of cotton, linen,silk, wool, rayon, cellulose esters such as cellulose acetate, nylons,polyesters such as polyethylene glycol terephthalate, acrylonitrilepolymers, vinylidene chloride polymers and other vinyl or acrylic esterpolymers; films, pellicles, sheets and other shaped articles of variousplastic systems such as of cellulose ethers or esters includinghydroxyethyl cellulose, methyl cellulose, cellulose acetate, celluloseacetate butyrate, polyesters such as polyethylene glycol terephthalate,nylons, vinyl chloride or vinylidene chloride polymers and copolymers,methyl methacrylate polymers and copolymers, aminoplast or phenoplastresin, organopolysiloxane resins or rubber.

The caulks of the present invention are particularly valuable in thatthey can be used directly on any of the substrates without the need of apriming coat.

The solvents used in the polymerization may be such organic solvents asbenzene, toluene, Xylene, solvent naphthas of aliphatic, aromatic, ornaphthenie type, such as mineral spirits, acetone, dioxane, etc. Ofcourse, other modes of polymerization can be used. The amount of solventin the final caulk is from percent to 30 percent based on total weight.Preferably, it is from percent to 15 percent.

The fillers are present in an amount of from percent to 90 percent byweight of the total solids in the composition depending upon theconsistency desired, the presence or absence of thickening agents, theamount and identity of solvent utilized, and so forth. Suitable fillersinclude calcite, limestone, mica, talc, asbestos fiber or powder,diatomaceous earth, barytes, alumina, slate flour, calcium silicate,clay, colloidal silica, magnesium carbonate, magnesium silicate, and soon. The amounts of solvent, if any, filler, and polymer solids are suchas to give the caulking composition a dough-like consistency.

Among the drying oils from which the drying oil fatty acid glycidylester is derived are linseed, tung, tall, safflower, isano, soya,dehydrated castor, maleinized or fumarized linseed, oiticica, palm,peanut, corn, walnut, menhaden, dehydrogenated castor, and cottonseedoils, and similar oils, as Well as acids not derived from drying oilsand of a synthetic origin, with a carbon chain having unsaturationtherein which can be caused to cure in a manner analogous to linseedoil. The preferred oils are those which contain oleic and linoleic acidsor linoleic and linolenic acids as the predominant ones. The preparationof the fatty acid glycidyl ester is carried out by wellknown proceduresas is the esterification of the carboxyl groups on the polymericbackbone. Exemplary of publications describing the preparation of asimilar polymer is British Pat. No. 1,060,711. The glycidyl ester may beprepared in the manner taught by U.S. Pat. 3,366,706. The British patentis the same type of polymer generally, although the products taughttherein have several defects making them unsuitable for many usesincluding caulking or sealing compositions. For example, all of thebackbone polymers disclosed are brittle or hard polymers. Thus, itappears that the softest polymer of the British patent is described inExample 6, and that would have a glass transition temperature (T ofabout 70 C. The most serious disadvantage is a lack of any recognitionof the importance of free carboxyl groups. Most of the examples utilizethe glycidyl ester in molar excess over the carboxyl groups. Someexamples, including Examples 2, 5, 6, 7, and 13 have a very slightexcess of carboxyl groups over epoxy groups reacted therewith, but thereis advanced no reason therefor. Most importantly, the only two examplesrelating to the use of unsaturated glycidyl esters, Examples 14 and 15,teach directly away from the present invention in requiring thatapproximately a 100 percent molar excess of the glycidyl ester beutilized over that required to react with all of the carboxyl groups inthe polymer. One of the most important disadvantages of this lack ofacid groups is that such polymers would be quite deficient in adhesionto various substrates.

It is essential that the glycidyl ester of an unsaturated fatty acid canbe reacted with the preformed polymer backbone containing carboxylgroups. The simultaneous polymerization of carboxyl-containing monomerssuch as acrylic acid with glycidyl esters such as glycidyl methacrylateis impractical because they react and crosslink in situ. Alsounsatisfactory is the scheme of forming a polymer with glycidyl groupsand then esterifying these with the unsaturated fatty acid. This againresults in a lack of free carboxyl groups which has a number ofdisadvantages. It is also important to limit the number of ester groups,because for every esterified carboxyl, a hydroxyl group is formed. Themore of these that are present the more likely the polymer is to besensitive to water in vapor or liquid form.

Any of the conventional driers, such as the linoleates, naphthenates,and resinates of cobalt, Zirconium, manganese, lead, cerium, chromium,iron, nickel, uranium, and zinc are suitable.

The amount of drier based on the weight of the glycidyl ester of Formula1V can be as low as 0.05 percent to as high as 3 percent or more. Bestresults are obtained with combinations of driers, particularly zincnaphthenate and cobalt naphthenate in quite small amounts, for example,from .05 percent to .5 percent of the zinc naphthenate are particularlyuseful. The amount of drier utilized should be such to minimize dirtpickup by the finished caulk.

It is helpful, in some cases, to utilize a silane to improve wetadhesion to glass by the caulk and also, at times, to utilizeplasticizers for providing low temperature flexibility, for example, at--15 F. Suitable silanes include vinyltriethoxysilane, 'ymethacryloxypropyltrimethoxysilane, -mercaptopropyltrimethoxysilane,-glycidoxypropyltrimethoxysilane, ,8- 3,4-epoxycyclohexyl)ethyltrimethoxysilane, 'y-aminopropyltriethoxysilane, andN-(dimethoxymethylsilylisobutyl)ethylenediamine. The silaneconcentration may be between about 0.05 percent and 0.5 percent. Higheramounts may be used but do not result in proportional improvements inadhesion. Suitable plasticizers include oil-modified sebacic acidalkyds, unmodified sebacic acid alkyds, oil-modified maleic polyesters,etc. It is preferred to use interna plasticization by means of softmonomers in the backbone. This pro vides a product which can be usedwith less solvent, thus minimizing shrinkage.

To assist those skilled in the art to practice the present invention,the following modes of operation are suggested by way of illustration,parts and percentages being by weight and the temperature in C. unlessotherwise specifically noted.

(1) A glass-block window is mounted in a wood frame within an opening ina stone wall of a house. The joint between the wood frame and the stonewall and the joint between the peripheral edge of the glass-blockassembly and the wood frame are filled with the caulking composition tobe tested. Aluminum-glass joints are also caulked. It is then aged andweathered. Accelerated tests are conducted in the laboratory at elevatedtemperatures.

EXAMPLE 1 Preparation of copolymer backbone Apparatus is providedequipped with a stirrer, thermometer, inlet and outlet tubes for gas,and a device for admitting reactants. The apparatus is swept withnitrogen and a slow current of this gas is maintained during thepolymerization cycle. There are charged to this apparatus 366.0 parts ofxyelne which is heated to C. At this reaction temperature, a mixture of2267.0 parts of butyl acrylate, 425.0 parts of methyl methacrylate, 70.6parts of acrylonitrile, 70.6 parts of methacrylic acid, 148.0 parts ofxylene, and 4.14 parts of a 75 percent solution of t-butyl peracetate inmineral spirits is added over a fivehour period. Subsequently there isadded 3.76 parts of t-butyl peracetate and 26.0 parts of xylene over athirty minute period. The reaction mixture is held at 140 C. for anadditional one hour to complete the process. The product is a clear,yellow solution having an approximate viscosity of 120,000 cps.Brookfield at 25 C., at approximately 83.0 percent solids. The monomerweight ratios used are:

EXAMPLE 2 Preparation of the glycidyl ester of linseed oil fatty acid Toa 3-liter glass reaction flask equipped with a stirrer, thermometer,reflux condenser, distillate receiver and nitrogen inlet were charged,310 parts of linseed oil fatty acid and 900 parts of xylene, undernitrogen. The mixture was heated to 125 C. and maintained at thistemperature during the addition of 216 parts of 25 percent sodiummethoxide in methanol over a 2 hour period with the simultaneous removalof methanol and xylene. Upon completion of sodium methoxide addition,the reaction temperature was increased to 130 C. and 463 parts ofepichlorohydrin and 5.2 parts of tetraethyl ammonium bromide were addedto the reaction mixture. The reaction temperature was maintained at 120C. for V2 hour and then cooled to 90 C. with the subsequent addition of175 parts of deionized water. The mixture was stirred at 90 C. for /2hour and then allowed to stand for /2 hour. The bottom layer was removedand top layer was distilled under vacuum at 20 mm. Hg to a pottemperature of 120 C. The liquid was cooled to 5 C. and filtered througha -20 micron filter. The total yield of product was 337 parts having aslight haze and amber color. A11 oxirane oxygen titer of 2.5 to 2.7meq./g. is typical for the product.

EXAMPLE 3 Preparation of a polymeric sealant from the reaction productof glycidyl fatty acid ester of linseed oil with a copolymer acidfunctionality (A) To a 5-liter reaction flask equipped with a stirrer,thermometer, condenser, and nitrogen inlet are charged 2758 parts of anacrylic resin (BA/MMA/AN/MAA; 80/ 15/2.5/2.5 wt. percent composition)having a solids content of 83.4 percent and an acid titer of 0.253meq./g. The acrylic resin is heated to 110 C. and 120.0 parts ofglycidyl fatty acid ester of linseed oil (with an oxiraneoxygen assay of2.56 meq./g.) and 2.92 parts of tetraethylammonium bromide are addedwith stirring, in a nitrogen atmosphere. The mixture is heated to 145 C.and maintained at 145 C. for 4 hours. The reaction product, aftercooling and filtering at 90 C., is clear amber solution with an acidtiter of 0.163 meq./g. at 84.5 percent solids which corresponds to 74.6percent coreaction.

(B) A coreaction product was prepared according to Example 3A from thefollowing reaction charge: 3036 parts of copolymer (A) and 272 parts ofglycidyl fatty acid ester of linseed oil of Example 2 above.

EXAMPLE 4 Preparation of a polymeric sealant from the reaction productof glycidyl fatty acid ester of soybean oil with a copolymer containingacid functionality To a 2-liter reaction flask equipped with a stirrer,thermometer, condenser, and nitrogen inlet are charged 900.0 parts of anacrylic resin (BA/MMA/AN/MAA: 80/ 15/ 2.5/2.5 wt. percent composition)having a solids content of 81.9 percent and an acid titer of 0.237meq./g. The acrylic resin is heated to 110 C. and 39.0 parts of glycidylfatty acid ester of soybean oil (with an oxirane-oxygen assay of 2.68meq./g.) and 0.895 part of tetraethyl ammonium bromide are added withstirring. The mixture is heated to 140 C. for four hours, after which,the reaction product is cooled and filtered at 90 C. The product is aclear amber solution with an acid titer of 0.124 meq./ g. at 83.2percent solids which corresponds to 92.8 percent coreaction.

EXAMPLE 5 Preparation of a polymeric sealant from the reaction productof glycidyl fatty acid ester of safllower oil with a copolymercontaining acid functionality To a 2-liter reaction flask equipped witha stirrer, thermometer, condenser, and nitrogen inlet are charged 900.0parts of an acrylic resin (BA/MMA/AN/MAA: 80/ 15/2.5/2.5 wt. percentcomposition) having a solids content of 81.6 percent and an acid titerof 0.236 meq./ g. The acrylic resin is heated to 110 C. and 39.0 partsof glycidyl fatty acid ester of safilower oil (with an oxiraneoxygenassay of 2.61 meq./g.) and 0.895 part of tetraethylammonium bromide areadded with stirring. The mixture is heated to C. for four hours, afterwhich, the reaction is cooled and filtered at 90 C. The product is aclear amber solution with an acid titer of 0.127 meq./g. at 83.1 percentsolids which corresponds to 91.5 percent coreaction.

EXAMPLE 6 A typical formulation for preliminary thin film evaluationprior to further evaluation as caulks is as follows:

Parts by weight Oil modified polymer (83 percent solids) 194 Pine OilNo. 230 e 2 Ethylene glycol 3.4 CaCO Ultrasbestos (floor tile grade) 6Texas Talc No. 2619 34 Cab-O-Sil M-5 d 10 Xylene 320 Cobalt naphthenate(6% Co 1% Co ba d on our.

0 The Glidden Company.

J ohnsManville.

c Whittaker, Clark and Daniels, Inc.

' Cabot Corporation, colloidal silica.

e Oil is material of Formula IV.

(A) The following results are obtained with the formulation, using theoil modified polymer of Example 3A cast into IO-mil test sheets whichare exposed to atmospheric air for one week at room temperature.

tensile: 96.7 p.s.i. elongation: 261 percent elastic recovery: 61percent (B) When the same 10-mil test sheet is exposed to hot air at 90C. for sixteen hours, rather than air drying at ambient temperature, theresults are as follows:

tensile strength: 75.9 p.s.i. elongation: 192 percent elastic recovery:81.5 percent (C) Repeating (A) but using the oil-modified polymer ofExample 3B gives the following results: tensile strength: 101 p.s.i.elongation: 137 percent elastic recovery: 97.5 percent (D) Repeating (B)but with the modified polymer of Example 3B gives the [following values:

tensile strength: 111 p.s.i. elongation: 117 percent elastic recovery:97.6 percent When the unmodified copolymer of Example 1 is used in thisformulation, the results are as follows:

Zinc naphthenate (8% Zn) (1% Zn based on oil). Cobalt naphthenate (6%Co) (0.15% Co based on oil).

11 (A) The following results are obtained for the above caulkformulation using the oil-modified polymer of Example 3A with the caulkbeing cast into inch thick test strips and exposed to hot air at 90 C.for one week.

tensile strength: 47.8 p.s.i. elongation: 204 percent elastic recovery:56.1 percent shore A hardness: 55

(B) The following results are achieved using the above caulk formulationusing the oil-modified polymer of Example 3A cast into A inch thick teststrips and exposed to atmospheric air at 20 to 25 C. for 3 months.

tensile strength: 14.8 p.s.i. elongation: 418 percent elastic recovery:73.8 percent EXAMPLE 8 (A) The following results are obtained for theabove caulk formulation using the oil-modified polymer of Example 3Bwith the caulk being cast into 4 inch thick test strips and exposed tohot air at 90 C. for one week.

tensile strength: 16.8 p.s.i. elongation: 262 percent elastic recovery:57.8 percent shore A hardness: 40

(B) The following results are achieved using the above caulk formulationusing the oil-modified polymer of Example 3B cast into inch thick teststrips and exposed to atmospheric air at 20 to 25 C. for 3 months.

tensile strength: 33.1 p.s.i. elongation: 256 percent elastic recovery:94.5 percent EXAMPLE 9 Another typical caulk formulation is:

Parts Polymer (83 percent total solids) 2336 Pine Oil No. 230 24Ethylene glycol 40 CaOO 1800 Ultrasbestos floor tile grade 72 Texas TalcNo. 2619 408 Cab-O-Sil M-5 120 Cobalt naphthenate (6 percentconcentration) 2.4 Zinc naphthenate (8 percent concentration) 12.1Xylene 216 Similar results to those of the foregoing examples areobtained.

Baker Castor Oil Company, Bayonne, NJ. b Union Carbide A-151 or A-174.

Mixing procedure (1) Prepare under nitrogen. (2) Charge Camel Carb,Texas Talc, Thixatrol ST,

titanium dioxide and mix for several minutes.

(3) Charge polymer and mix for 50 minutes.

(4) Slurry driers and silane into xylene and add to sealant, mix for 10minutes.

(5) Package under nitrogen atmosphere.

Using this formulation, excellent dry and wet adhesion to glass isobtained, and the caulk has excellent properties.

In the above Examples 3 to 5 wherein glycidyl fatty acid ester oflinseed oil, soybean oil, and safliower oil are mentioned, the glycidylesters of the fatty acids derived from said oils (not the oilsthemselves) is the meaning to be given the quoted phrases. Similarly, inexamples mentioning oil modified polymer, the meaning to be given thephrase is that the polymer has been modified by having carboxyl groupsesterified by reaction with the glycidyl ester of the specified fattyacid.

I claim:

1. A fluent caulking composition having about 10 to weight percent,solids basis, of an addition polymer having a backbone of copolymerizedethylenically unsaturated monomers, one of which is an unsaturatedcarboxylic acid monomer, the backbone having the formula:

l iifl F L if] Kine wherein R is H, lower alkyl, halogen, CH COOR,-COOR, or -CH COOH, R being lower alkyl of from 1 to 8 carbon atoms;

R being at least one of H, or at least one lower alkyl radical havingfrom 1 to 8 carbon atoms, at least a portion of R being H, to give freecarboxyl groups;

R is an unsaturated, air curable alkyl radical;

R is H, -COOH-, or CONH or COOR, wherein R is as above;

X is derived from at least one other vinyl monomer and is optional;

the units in parentheses being in any order, which polymer is derivedfrom the esterification of some of the carboxylic groups in saidbackbone by at least one unsaturated fatty acid glycidyl ester, theamount of said unsaturated carboxylic acid in the backbone, beforemodification, being from 0.25 to 25 weight percent on the basis ofcopolymerized monomers, the molar ratio of free carboxyl groups toglycidyl ester groups, before modification of the backbone, being fromabout 1:0.9 to 1:02, in which the polymer is a rubbery material and theT of the backbone polymer free of pendant ester groups is below about 10C., and a pigment or filler in Lheamount of about 20 to weight percenton a solids asis.

2. The caulking composition of claim 1 wherein the polymer is such thatR is H, R is H or lower alkyl having 1 to 5 carbons, R has about 10 to22 carbon atoms, the amount of said unsaturated carboxylic acid is from1 to 5 weight percent of the backbone monomers,

14 no more than about 5 percent by weight of the units References Citedhavmg the fmmma UNITED STATES PATENTS g 1 3,442,873 4/1969 Vasfer 260-7s.s 3,366,706 11/1968 Vasfer 260834 5: 3,583,955 6/1971 Holicky260-784 3,448,089 6/1969 -Aleste 26078.5 3,242,123 4/1966 Mayfield260-296 R2 10 FOREIGN PATENTS 5:0 1,060,711 4/1967 Great Britain.

b h dlfi d 1 d d t OTHER REFERENCES eing present in t e mo e p0 ymer, ansai ra io 1s from 1:017 to 1:03. Silane Coupling Agents, SlermanIndustrial & Eng,

3. The caulking composition of claim 2 in which the Chemistry March 19663337' amount of said unsaturated carboxylic acid in the poly- ALLANLIEBERMAN Primary Examiner mer is 1.5 to 3.5 weight percent of saidbackbone, and

said ratio is 1:0.6 to 1:0.4, and the T of the backbone ZAITLEN,Assistant Examiner gobmer free of pendant ester groups is below aboutUS. CL XIR- 4. The caulking composition of claim 3 in which the 26041 B,41 C, 78.5 T, 88.1 PC T of said polymer is below -10 C.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO.3,786,020 DATED January 15, 197+ INVENTOR(S) William D. Emmons It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below;

In Column line 31, change "0, m, or p" to g, m, or p.

In Column 5, line '72, change "l to l In Column 13, following line 22,enter the following:

Claim 5. The composition of claim 2 in which an organic solvent ispresent, andthe polymer is predominantly an ester of acrylic acid and analkanol having 1 to carbon atoms, with an ester of methacrylic acid andan al'xanol having 1 to carbon atoms, methacrylonitrile oracrylonitrile, and methacrylic acid or acrylic acid being present insmaller amounts.

Claim 6. The composition of clairn in which an organic solvent ispresent, and the polymer is predominantly an ester of acrylic acid andan alkanol having 1 to r carbon atoms, with an ester of methacrylic acidand an alkanol having 1 to carbon atoms, methacrylonitrile oracrylonitrile, and methacrylic acid or acrylic acid being present insmaller amounts.

Claim 7. The composition of claim 6 raring a silane therein.

Signed and Sealed this twenty-ninth Day Of July 1975 [SEAL] A ttest:

RUTH C. MASON C. MARSHALL DANN 1 Nesting Officer ('ummissrmwr nj'lalenlsand Trademarks

